EP0125641B1 - Alkanoyloxybenzenesulfonate salt production - Google Patents

Alkanoyloxybenzenesulfonate salt production Download PDF

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Publication number
EP0125641B1
EP0125641B1 EP84105303A EP84105303A EP0125641B1 EP 0125641 B1 EP0125641 B1 EP 0125641B1 EP 84105303 A EP84105303 A EP 84105303A EP 84105303 A EP84105303 A EP 84105303A EP 0125641 B1 EP0125641 B1 EP 0125641B1
Authority
EP
European Patent Office
Prior art keywords
hydroxy
benzenesulfonic acid
phenyl
sodium salt
salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP84105303A
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German (de)
English (en)
French (fr)
Other versions
EP0125641A2 (en
EP0125641A3 (en
Inventor
Bonnie Gary Mckinnie
Gene Conrad Robinson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ethyl Corp
Original Assignee
Ethyl Corp
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Filing date
Publication date
Application filed by Ethyl Corp filed Critical Ethyl Corp
Priority to AT84105303T priority Critical patent/ATE25674T1/de
Publication of EP0125641A2 publication Critical patent/EP0125641A2/en
Publication of EP0125641A3 publication Critical patent/EP0125641A3/en
Application granted granted Critical
Publication of EP0125641B1 publication Critical patent/EP0125641B1/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof

Definitions

  • This invention relates to the production of alkali metal and alkaline earth metal salts of certain acyloxybenzenesulfonates, and more particularly to the manufacture of these salts by reaction between the corresponding salts of hydroxybenzenesulfonic acid and aryl esters.
  • the acyloxybenzenesulfonate salts of the present invention have many applications. For example, they are used in the textile industry as activators for the peroxide bleaching of fabrics and as dyeing assistants in the dyeing of acrylic fibers.
  • the present invention contemplates the production of sodium 4-nonanoyloxybenzenesulfonate in accordance with the following equation:
  • the invention contemplates the production of alkali metal and alkaline earth metal salts of acyloxybenzenesulfonates of the formula: in which R is a hydrocarbyl radical containing up to 30 carbon atoms and is selected from alkyl, alkenyl, cycloalkyl, aryl, aralkyl and M is an alkali metal or an alkaline earth metal by reacting at elevated temperature the corresponding hydroxybenzene sulfonate salt of the formula: with an aryl ester of the formula: in which R and M are as defined above.
  • aryl esters used are known to the art as are methods for their preparation.
  • U.S. Pat. No. 2,467,206 to Gresham et al., issued 12 April 1979 discloses the synthesis of aryl esters of the formula acylOR, R representing an aryl group attached to phenolic hydroxyl in phenol by heating an organic compound containing non-aromatic olefinic unsaturation with carbon monoxide and a phenol at elevated temperature and pressure in the presence of a catalyst containing, as an essential ingredient, cobalt or nickel.
  • Aelony "Direct Esterification of Phenols with Higher Fatty Acids", Journal of the American Oil Chemists' Society, 32, 170-172 (1955), discloses a method of preparing fatty acid esters of many monohydric and dihydric phenols by direct esterification of the phenols with higher fatty acids at reaction temperatures between 115-290°C., optionally in the presence of catalysts such as sulfuric acid, phosphoric acid, zinc stearate, lead stearate and triphenyl phosphite.
  • catalysts such as sulfuric acid, phosphoric acid, zinc stearate, lead stearate and triphenyl phosphite.
  • the hydroxybenzenesulfonate salts which may be used in accordance with this invention are salts of the formula: wherein M is an alkali metal or an alkaline earth metal.
  • the metal sulfonate functional group can be bonded to any of the aromatic carbon atoms either ortho-, meta- or para- to the hydroxyl group in the ring.
  • the hydroxybenzenesulfonate salts used are known compounds and can be prepared by methods known to the art, such as, for example, by treating phenol with sulfuric acid in the presence of boron fluoride at elevated temperature as described by R. J. Thomas, et al., "Sulfonation and Nitration Reaction Promoted by Boron Fluoride", Industrial and Engineering Chemistry, 32, 408-410 (1940).
  • hydroxybenzenesulfonate salt reactants are:
  • acyl ester reactants which may be used in the present invention are:
  • acyloxybenzenesulfonate salt products of the present process are:
  • the process of the invention is carried out by heating the mixture of aryl ester and the alklai metal or alkaline earth metal salt of hydroxybenzenesulfonic acid in a suitable reaction vessel.
  • the process is carried out at a temperature of from 200 to 350°C., more preferably, 250 to 325°C.
  • the process be carried out under substantially anhydrous conditions, and accordingly, the components of the reaction system are brought together and maintained under a substantially dry, inert atmosphere. It is not necessary, however, that the reagents used in the process be anhydrous before they are combined as any water present in the reagents can be removed therefrom by conventional techniques, such as, for example, by azeotropic distillation of the combined reagents using an organic solvent such as hexane, octane, toluene and xylenes.
  • an organic solvent such as hexane, octane, toluene and xylenes.
  • oxygen-containing compounds other than the desired acyloxybenzenesulfonate salts are produced by the process of the invention.
  • Phenol and disodium phenol-2,4-disulfonate are the primary byproducts formed by the reaction.
  • the yield of acyloxybenzenesulfonate salt may be as high as 90 weight percent and above. Removal of phenol from the reaction mixture is readily effected by distilling as rapidly as it is formed. Since the reaction is an equilibrium reaction, removal of the phenol helps to drive the reaction to completion.
  • the use of a fractionating column is not necessary. However, in those instances where an aryl ester reactant used in the process has a boiling point close to that of phenol, the use of a fractionating column is desirable.
  • the relative proportion of reactants employed by the reaction may be the stoichiometrically required quantities although other proportions may be employed if desired. It is preferred to use an excess of aryl ester in the reaction since the use of greater than stoichiometric quantities of ester also serves to drive the reaction to completion. Excellent results are obtained when the mole ratio of aryl ester to hydroxybenzenesulfonate salt is 1.25 to 5:1.
  • the reaction is carried out at atmospheric pressure, however, higher pressures up to 6895 kPa (1000 psig), or higher, can be used if desired.
  • the maximum pressure is limited only by the strength of the retaining vessel.
  • the reaction may be carried out at subatmospheric pressures to facilitate distillation of by-product phenol.
  • an inert liquid may be employed as a reaction medium.
  • the reaction may be conducted satisfactorily in the absence of any added medium, especially, if an excess of aryl ester reactant is used in the process.
  • a solvent it is advantageous, but not necessary, that the solvent have a boiling point higher than the by-product phenol produced by the process and lower than the aryl ester reactant. In this manner, it is possible to distill off substantially all of the unwanted phenol while preventing the aryl ester reactant from distilling off during the reaction.
  • solvents which may be used in the process include the chlorinated benzenes, the chlorinated toluenes, higher boiling alkanes such as decane, undecane, tetradecane, hexadecane, mineral oil and mixtures of higher boiling linear and branched alkanes.
  • aprotic solvents such as triglyme, tetraglyme, 1,2-diethoxyethane and dipolar aprotic solvents such as N,N-dimethylacetamide, tetramethylene sulfone, N-methylpyrrolidinone and like materials may also be used.
  • the acyloxybenzenesulfonate salts produced by the process are easily separated from unreacted aryl ester and solvent which remain after the removal of by-product phenol.
  • the reaction mixture is filtered and the solid product washed free of aryl ester and solvent by the use of a low boiling solvent such as heptane, toluene, dichloromethane or diethyl ether. The low boiling solvent is then removed by evaporation from the solid product.
  • the acyloxybenzenesulfonate salt product may be separated from the reaction mixture by dissolving it in water in which the reaction solvent and aryl ester reagents are generally insoluble, separating the organic and aqueous phases thus formed and separating the acyloxybenzenesulfonate salt from the aqueous phase by known techniques such as crystallization or spray drying.
  • Heptanoic acid (180.9 g; 1.39 mol), phenol (180.69 g; 1.92 mol), toluene (216.5; 2.35 mol) and sulfuric acid (5.04 g; 0.0514 mol) were charged to a 2-liter, 3-necked round bottom flask equipped with a thermometer, a magnetic stirrer and an 8" Vigreux column equipped with a Dean-Stark trap.
  • the reaction mixture was heated to 131°C. and maintained at that temperature for five hours to give 74 weight percent phenyl heptanoate.
  • the reaction product was washed once with a solution of 0.08 mol Na 2 C0 3 in 4.5 mol water. Phase separation occurred after approximately 20 minutes.
  • the organic layer was fractionally distilled at atmospheric pressure using a 20-plate Oldershaw column to remove phenol and toluene. The remaining liquid was then distilled through a 10-plate Oldershaw column at 50 torr to give a center cut fraction of 154.4 g (54% yield) of pure phenyl heptanoate.
  • a 1-liter, 3-necked round bottom flask equipped with a mechanical stirrer, thermocouple well and a Dean-Stark trap was charged with sodium 4-hydroxybenzenesulfonate dihydrate (160 g; 0.670 mol), hexadecane (102 g), and octane (166 g).
  • the reaction mixture was refluxed until 15 mLs of water had been collected in the trap.
  • a 16 mm x 300 mm Vigreux column was then attached between the reaction flask and the trap and distillation was continued until 100 mLs of octane had been collected by intermittently draining the trap over a period of time of 1.5 hours.
  • the flask was cooled slightly and phenyl nonanoate (428.5 g; 1.38 mol) was added to the flask and the remaining octane was removed by distillation.
  • the resulting mixture was refluxed over the Dean-Stark trap at a pot temperature of 292°C, and an overhead temperature between 180 and 282°C., inclusive.
  • the trap was occasionally drained to remove phenol.
  • approximately 70 mLs of phenol and approximately 60 mLs of hexadecane were collected.
  • the pot temperature was 301°C and the overhead temperature fluctuated between 275 and 282°C.
  • the mixture was cooled and the solid was collected by filtration and washed on the filter with approximately 100 mLs of octane.
  • the filter cake was reslurried in approximately 400 mLs of a mixture of hexane and diethyl ether, collected and then reslurried a second time in approximately 400 mLs of a mixture of pentane and diethyl ether.
  • the remaining solid was collected by vacuum filtration, washed with pentane and dried in an oven at 90°C to give 214.5 g of a white solid.
  • Analysis by cationic titration indicated that the product consisted of 86.9 weight percent benzenesulfonic acid, 4-hydroxynonanoate, sodium salt.
  • Analysis by NMR indicated that the product also contained 2.8% by weight disodium phenol-2,4- disulfonate with the remainder of the product consisting of sodium 4-hydroxybenzenesulfonic acid.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP84105303A 1983-05-11 1984-05-10 Alkanoyloxybenzenesulfonate salt production Expired EP0125641B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84105303T ATE25674T1 (de) 1983-05-11 1984-05-10 Herstellung von alkanoyloxybenzolsulfonat-salzen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/493,452 US4537724A (en) 1983-05-11 1983-05-11 Alkanoyloxybenzenesulfonate salt production
US493452 1983-05-11

Publications (3)

Publication Number Publication Date
EP0125641A2 EP0125641A2 (en) 1984-11-21
EP0125641A3 EP0125641A3 (en) 1985-07-31
EP0125641B1 true EP0125641B1 (en) 1987-03-04

Family

ID=23960287

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84105303A Expired EP0125641B1 (en) 1983-05-11 1984-05-10 Alkanoyloxybenzenesulfonate salt production

Country Status (6)

Country Link
US (1) US4537724A (enrdf_load_stackoverflow)
EP (1) EP0125641B1 (enrdf_load_stackoverflow)
JP (1) JPS6041659A (enrdf_load_stackoverflow)
AT (1) ATE25674T1 (enrdf_load_stackoverflow)
CA (1) CA1212122A (enrdf_load_stackoverflow)
DE (1) DE3462498D1 (enrdf_load_stackoverflow)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3524052A1 (de) * 1985-07-05 1987-01-08 Hoechst Ag Verfahren zur herstellung von acyloxybenzolsulfonsaeuren und deren salzen
GB8523962D0 (en) * 1985-09-28 1985-10-30 Interox Chemicals Ltd Preparation of sulphophenyl esters
DE3538143A1 (de) * 1985-10-26 1987-04-30 Hoechst Ag Verfahren zur herstellung von acyloxibenzolsulfonsaeuren und deren salzen
DE3538141A1 (de) * 1985-10-26 1987-04-30 Hoechst Ag Kontinuierliches verfahren zur herstellung von acyloxybenzolsulfonsaeuren
EP0270304B1 (en) * 1986-12-05 1991-07-24 Interox Chemicals Limited Ester manufacture
GB8712909D0 (en) * 1987-06-02 1987-07-08 Interox Chemicals Ltd Preparation of esters
DE3824901A1 (de) * 1988-07-22 1990-02-15 Hoechst Ag Verfahren zur herstellung von acyloxibenzolsulfonsaeuren oder deren salzen
US5300665A (en) * 1992-09-16 1994-04-05 Rhone-Poulenc Surfactants And Specialties, L.P. Process for preparing fatty acid esters and amides of sulfonic acid salts
US6069262A (en) * 1997-10-06 2000-05-30 Finetex, Inc. Fatty acid esters of hydroxyalkyl sulfonate salts and process for producing same
US6448430B1 (en) 1999-09-10 2002-09-10 Eastman Chemical Company Process for the preparation of aryl carboxylate esters
US6448431B1 (en) 1999-09-13 2002-09-10 Eastman Chemical Company Production of aryl carboxylate esters
US6362145B1 (en) 2000-11-14 2002-03-26 Clariant International Ltd. Clear soap bar comprising metal catalyst sodium cocoyl isethionate
DE10233827A1 (de) 2002-07-25 2004-02-12 Clariant Gmbh Verfahren zur Herstellung von Acyloxybenzolsulfonaten
US6790981B2 (en) * 2002-12-13 2004-09-14 Clariant Finance (Bvi) Limited Process for the preparation of acyloxybenzenesulfonates
DE10300981A1 (de) * 2003-01-14 2004-07-22 Clariant Gmbh Verfahren zur Herstellung von Acyloxybenzolsulfonaten
WO2006137473A1 (ja) * 2005-06-24 2006-12-28 Nissan Chemical Industries, Ltd. 芳香族スルホン酸化合物の製造法
DE102007026216A1 (de) * 2007-06-05 2008-12-11 Clariant International Ltd. Feste Partikel von hydrophoben Bleichaktivatoren

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2337924A (en) * 1937-05-08 1943-12-28 Gen Aniline & Film Corp Aromatic sulphonic acids having capillary-active properties and a process of preparing them
US3023183A (en) * 1959-06-29 1962-02-27 Cuban American Sugar Company Esterification
CH481045A (de) * 1962-12-07 1969-11-15 Chemische Werke Witten Gmbh Verfahren zur Herstellung von Arylestern
US3394155A (en) * 1964-05-22 1968-07-23 Lever Brothers Ltd Preparation of surface-active agents
US3636016A (en) * 1969-05-28 1972-01-18 Continental Oil Co Surface active agents
CH550279B (de) * 1971-12-21 1974-06-14 Ciba Geigy Ag Verfahren zum faerben von textilfasermaterial aus polyacrylnitril.
CH563356A5 (enrdf_load_stackoverflow) * 1972-05-17 1975-06-30 Esteve Dr Lab Del Sa
EP0008061B1 (de) * 1978-08-08 1981-07-29 Ciba-Geigy Ag Neue halogenierte Phenolester, diese enthaltende antimikrobielle Mittel und deren Verwendung
US4255555A (en) * 1979-06-04 1981-03-10 Hooker Chemicals & Plastics Corp. Transesterification process for preparation of linear polyesters
EP0105672B1 (en) * 1982-09-28 1986-04-09 The Procter & Gamble Company Synthesis of sulphonated organic compounds

Also Published As

Publication number Publication date
CA1212122A (en) 1986-09-30
JPH0321541B2 (enrdf_load_stackoverflow) 1991-03-22
US4537724A (en) 1985-08-27
EP0125641A2 (en) 1984-11-21
DE3462498D1 (en) 1987-04-09
ATE25674T1 (de) 1987-03-15
EP0125641A3 (en) 1985-07-31
JPS6041659A (ja) 1985-03-05

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